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LECTURE11:
INDUSTRIAL GASES (H2, N2, O2, CO2,
ACETYLENE, ETC.)
ACETYLENE: INTRODUCTION
Acetylene
Properties
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Molar mass
26.04 g mol1
Appearance
Colourless gas
Odour
Odourless gas
Density
Melting point
80.8C
Triple pointat 1.27 atm
Sublimation
conditions
84 C (1 atm)
Solubility
Vapor pressure
http://en.wikipedia.org/wiki/Acetylene
ACETYLENE: CHARACTERISTICS
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ACETYLENE: TIMELINE
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Berthelot
ACETYLENE: APPLICATIONS
For the chemical manufacture of
acrylonitrile,
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etc.
acetaldehyde, trichloroethylene, acetic acid, polyvinyl
alcohol, perchloroethylene etc.
propagryl alcohol, butyrolactone, vinyl pyrrolidine
etc.
ACETYLENE: PROCESSES
2.
3.
Calcium carbide
Paraffin hydrocarbons by pyrolysis (Wulff
process)
Natural gas by partial oxidation (Sachasse
process)
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1.
ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
Raw materials
Basis:
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ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
There are two methods for the acetylene
manufacture from calcium carbide
1.
2.
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Wet process
Dry process
Wet process,
.Calcium
ACETYLENE:
ACETYLENE FROM CALCIUM CARBIDE
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Dry Process
ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
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Animation:
http://nptel.ac.in/courses/103106108/downloads/swf%20file/Acetylene%20fro
m%20calcium%20carbide.swf
ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
Dry process
Equal
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ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
The crude acetylene gas containing traces of H2S,
NH3 and phosphine (PH3) form generator is
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either
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ACETYLENE:
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Raw materials
Basis: 1000kg acetylene (100%)
Natural gas
262000 Scf
Steam (600psig)
26308 kg
Electricity 140 kWH
Cooling water 25000 gal
Process water 200 gal
Solvent (make up) 2.95 kg
Reaction
C4H10 C2H2 + C2H4 + CO + H2
C 2 H4 C 2 H2 + H 2
2CH4 C2H2 + 3H2
(H = + 96.7kcals)
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ACETYLENE:
ACETYLENE:
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Animation:
http://nptel.ac.in/courses/103106108/downloads/swf%20file/Acetylene%20by%2
0wulff%20process.swf
ACETYLENE:
First, the hydrocarbon feed is diluted with steam (up to 1:8 ratios).
Pyrolysis is performed in a Wulff regenerative furnace, which is a
rectangular steel box filled with refractory bricks checker work.
The feed is carried through the chamber at sub-atmospheric pressure by
virtue of a large vacuum pump, thereby reducing the residence time as
small as 0.03 s.
Cracked gases leaves the chamber at about 370C.
The maximum temperature in the furnace just after the heating cycle
approaches 1315C.
The furnace is operated in four minutes cycle in which the checker work is
first heated for one minute and then feed gas pyrolyzed for one minute.
The same sequence of operation is then done in reverse direction through
the furnace. To facilitate reversal of the gas flow, fuel gas burners and
hydrocarbon feed pipes are located on each side of the combustion chamber.
To allow continuous flow of cracked gases to the purification train, two
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furnaces are usually operated on staggered cycles.
ACETYLENE:
By
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ACETYLENE:
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The
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ACETYLENE:
22.5
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ACETYLENE:
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Raw materials
Basis:
1000kg acetylene (99.5%) plus 340000 Cu ft. off gas (345 Btu/Cu ft.)
Natural gas
190000 Sef
Oxygen (95%) 5400 kg
Solvent
2.3 kg
Power 15000 kWH
Steam 4535.9 kg
Cooling water 22710 liter
Reaction
CH4 + 2O2 CO2 + 2H2O
2CH4 C2H2 + 3H2
(H = + 79.8 kcals)
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ACETYLENE:
ACETYLENE:
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ACETYLENE:
Mixing chamber
Flame room
Quench chamber
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ACETYLENE:
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CARBON DIOXIDE
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CARBON DIOXIDE
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In 7th century, Jan Baptist Van Helmont observed that during burning
of charcoal in the closed vessel, the mass of the resulting ash was
much less than that of the original charcoal.
In 1750 Joseph Black studied the Carbon dioxides properties by
treating limestone with acids to yield a gas (fixed air).
He
observed that gas was denser than air and supported neither flame nor
animal life.
when the gas is bubbled through an aqueous solution of lime, it would
precipitate calcium carbonate.
CO2
Molecular weight
: 44.01gm/mole
Appearance
: Colourless gas
Odour
: Odourless gas
Boiling point
: 57 0C
Melting point
: 78 0C
Density (1 atm and 00C): 1.977 kg/m3
Solubility
:
Soluble in water
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Raw materials
Coke or coal
Air
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Reaction
C + O2 CO2 (10 to 18% Pure) H = 23.16 kcals
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345 0C
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The amine solution, rich in CO2, passes out of the bottom of the
tower and through heat exchanger, where it is preheated by hot,
lean solution returning from the re-activator.
Then solution passes countercurrent to a stream of CO 2 and
steam, which strips CO2 out of the solution.
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operating cost
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Reverse reaction will proceed when heat is applied and is carried out in lye boiler.
A heat exchanger serves to preheat the strong lye as it approaches the boiler and
cool the weak lye returning to the absorber.
Additional weak lye cooling is accomplished in lye cooler to permit the reaction to
proceed further to the right in the absorber.
CO2 gas and water vapour released from the solution in the boiler pass through
steam condenser where the water condenses out and returns to the system.
The cool CO2 proceeds to the gas holder and compressors.
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POTASSIUM CARBONATE
PROCESS
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POTASSIUM CARBONATE
PROCESS
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CARBON DIOXIDE:
PURIFICATION OF LOW % CO2 CONTAINING GAS
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Hot CO2 gas, with low concentration (18%), passes through a heat
exchanger to lower the temperature.
It is then scrubbed with water to remove SO2 and dust particles.
The gas is further scrubbed in packed towers where, it is scrubbed
with Na2CO3 solution and absorbed in it to form NaHCO3 solution in
second tower.
Solution is heated in heat exchanger to remove absorbed CO2. ,
which is further cooled in cooler and stored.
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CARBON DIOXIDE:
PURIFICATION OF LOW % CO2 CONTAINING GAS
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CARBON DIOXIDE:
PURIFICATION OF HIGH % CO2 CONTAINING GAS
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CARBON DIOXIDE:
PURIFICATION OF HIGH % CO2 CONTAINING GAS
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Nitrogen (N2)
78.01
Oxygen (O2)
20.99
0.03 0.07
Argon (Ar)
0.94
Hydrogen (H2)
0.01
Neon (Ne)
0.0015
Exceptand
CO2Krypton
the concentration
of all0.01
the gases
Helium
(He and Kr)
0.02 listed above are
present in air are constant.
Also, water vapours and traces of ozone and iodine are present in
air in variable amounts.
The composition of air also depends on altitude and distance to
sea, in neighbourhood of industry, built up urban areas, nearby
volcanic phenomena.
Other gases such as CO, H2S and NO2 are also present in air.
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Gas
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Critical pressure
The
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No.
Critical Temperature
Critical Pressure
(0C)
(atm)
1.
Ethylene
+9.5
50.65
2.
Methane
82.85
45.6
3.
Nitrogen
147.13
33.49
4.
Hydrogen
239.9
12.8
5.
Oxygen
118.75
49.7
6.
Acetylene
+35.5
61.55
7.
Ammonia
+132.5
112.3
8.
Carbon monoxide
138.7
34.6
9.
Carbon dioxide
+31.3
72.9
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Sr.
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AIR
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Outer coil
Inner coil
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AIR
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AIR
Now as the cooled air suddenly expands through the nozzle, the
air suffers cooling, the temperature becomes lower than in the
first operation.
The colder air now passes through the outer coil producing an
atmosphere of lower temperature.
Hence when the cooled compressed air passes repeatedly through
the inner coil and subsequently undergoes Joule-Thomson effect,
the temperature of the air further drops.
In this way progressive cooling takes place until the temperature
of air falls below the critical temperature of oxygen and nitrogen.
During this process, the air undergoes liquefaction in the inner
coil, so on opening the valve liquid air falls in the container.
A part of liquid air evaporates, through the outer coil,
maintaining the low temperature below the critical temperature. 53
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Process diagram for Lindes process
LINDES PROCESS
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LINDES PROCESS
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LINDES PROCESS
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LINDES PROCESS
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CLAUDE PROCESS
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70%
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Processes
Linde
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PROPERTIES OF O2 AND N2
Molecular formula : O2
Molecular weight : 32gm/mole
Odour : Odourless
Nitrogen
Molecular formula : N2
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Oxygen
Density : 1.251gm/L
(00C,101.325kPa)
O2 AND N2 APPLICATIONS
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Oxygen
It is used to produce
oxyacetylene flame to
cutting and welding the
metals
In L.D. process for steel
production
For artificial respiration
in case of patients
For mountain climbers
and high attitude aero
planes flights
Nitrogen
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ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin
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